Polymers, method of producing the same and use of the same

ABSTRACT

N-Oxides of nitrogenous heterocycle or nitrogenous fused heterocycle polymers of general formula (1) or (7) (wherein any two of a, b, c, d, e, f, g and h are carbon atoms participating in the bonding between repeating units; at least one of them is N→O; the rest are each CH, N or N→O; and the degree of polymerization “n” is at least 5). These polymers have excellent heat resistance, are soluble in aqueous or organic solvents and controllable in the degree of depolarization and electrochemical redox potential, exhibit clear color changes by chemical or electrochemical oxidation or reduction, and are conductive per se . They can be used as moldings such as fibers and films; electrochromic elements; active materials and electrodes of cells; semiconductors including n-type semiconductors; and so on.

TECHNICAL FIELD

The present invention relates to N-oxidized poly (nitrogen-containingheterocyclic ring) and N-oxidized poly(nitrogen-containing condensedheterocyclic ring) which have excellent heat resistance, which aresoluble in aqueous solvents or organic solvents, active inelectrochemical oxidation and reduction whose potential can becontrolled, color of which clearly changes by chemical orelectrochemical oxidation-reduction, and which show conductivity bythemselves, a method of producing the same, and use of the same.

BACKGROUND ART

Poly(arylene) having a structure that aromatic rings are serially bound,particularly poly(arylene) having serially π conjugated system along themain chain (for example, poly(p-phenylene), poly(2,5-thienylene), andpoly(1,4-naphthalenediyl)) generally possess excellent heat resistance.Further, it is known that addition products of these poly(arylene) toelectron acceptors (e.g., AsF₅, etc.) or electron donors (e.g., lithium,sodium, etc.) have conductivity and have property to change their colorreversibly (electrochromic) by electrochemical oxidation-reduction so asto be available as materials for displays (for example, High polymers,Japan 38, 1080 (1989)). Japanese Patent Application Laid-Open No.Hei1-210420 discloses conductive substances produced by reducing polymershaving serial π conjugated system along the main chain and groupscomposed of 6-membered heterocyclic ring units, for example, a2,5-pyridinediyl group as a repeating constitutive unit. Japanese PatentApplication Laid-Open No.Hei 5-70565 discloses poly(quinolinediyl) andpoly(isoquinolinediyl), which are composed of condensed heterocyclicring units and Japanese Patent Application No. Hei 6-56972 disclosesquaternary poly(quinolinediyl) and poly(isoquinolinediyl).

However, most of the poly(arylene)s conventionally proposed show lowsolubility in water or organic solvents and are not melted, whichrestricts their application and is an obstacle to elicit theircharacteristic functions. With respect to the above-describedpoly(arylene)s, it has been desired to modify the molecular structure soas to develop such substances as having properties different from theconventionally known poly(arylene)s. For example, if it is possible toobtain poly(arylene) that has oxidation-reduction potential or changesits color (electrochromic phenomenon), different from the knownpoly(arylene)s, it would be used as an electrode to provide anelectrochromic display which has characteristics different from theconventionally used electrochromic indicative material (for example,“OYO BUTURI”, Vol.56, 1433 (1987)) or it would be used as an activematerial or an electrode to provide a polymer battery that hascharacteristics different from the known polymer battery (for example,“Denki Kagaku (Journal of the Electrochemical Society of Japan)” 54, 306(1986)). In order to confer conductivity on poly(arylene)s, it isnecessary to effect oxidation (p-doping) or reduction (n-doping) ofpoly(arylene)s that are usually in a neutral state (cf. theabove-described portions of OYO BUTURI and Denki Kagaku (Journal of theElectrochemical Society of Japan)). This oxidation-reduction isdisadvantageous in that a corrosive oxidizing agent such as iodine isused, that the process is complicated, and that dopants such as I⁻, ClO₄⁻, or NR₄ ⁺ may possibly render poly(arylene), which becomes conductive,chemically and physically unstable. Accordingly, it has been desired todevelop materials made of poly(arylene)s or its derivatives having nosuch a dopant and showing conductivity by themselves.

DESCRIPTION OF THE INVENTION

Under these circumstances, the present invention was completed as aresult of intensive investigation to screen poly(arylene)s having anovel molecular structure.

An object of the present invention is to provide poly (arylene),particularly N-oxidated (nitrogen-containing heterocyclic ring) polymerand N-oxidated (nitrogen-containing condensed heterocyclic ring)polymer, which have excellent heat resistance, which are soluble inaqueous solvents or organic solvents, depolarization and electrochemicaloxidation-reduction potential of which can be controlled, color of whichclearly changes by chemical or electrochemical oxidation-reduction, andwhich show conductivity by themselves.

Another object of the present invention is to apply such a novelN-oxidated poly(nitrogen-containing heterocyclic ring) and N-oxidatedpoly(nitrogen-containing condensed heterocyclic ring) to moldings suchas fiber or film, an electrochromic element, an active material or anelectrode for a battery, semiconductor, n-type semiconductor, and thelike.

The N-oxidated poly(nitrogen-containing heterocyclic ring) is a polymercontaining a polymer chain represented by the formula (1):

wherein two of any of a, b, c, d, e, and f represent carbon atoms thatare involved in binding between repeating units, at least one of themrepresents an N→O group, the remainings independently represent a CHgroup or a nitrogen atom, the maximum total number of the N→O groupsresented by a, b, c, d, e, and f is 2, the maximum total number of thenitrogen atoms is 3, and the degree of polymerization n is at least 5,or a polymer containing a polymer chain represented by the formula (2):

wherein two of any of a, b, c, d, e, and f represent carbon atoms thatare involved in binding between repeating units, at least one of themrepresents an N→O group, the remainings independently represent a CHgroup or a nitrogen atom, the maximum total number of the N→O groupsrepresented by a, b, c, d, e, and f is 2, the maximum total number ofthe nitrogen atoms is 3, two of any of o, p, q, r, s, and t representcarbon atoms that are involved in binding between repeating units, theremainings independently represents a CH group or a nitrogen atom, themaximum total number of the nitrogen atoms represented by o, p, q, r, s,and t is 3, and the degree of polymerization 1+m is at least 5.

The polymer of the above formula (1) is a polymer mainly containing arepeating unit of a nitrogen-containing heterocyclic ring whose nitrogenatom is oxidated, while the polymer of the above formula (2) is acopolymer containing a repeating unit of a nitrogen-containingheterocyclic ring whose nitrogen atom is oxidated and a repeating unitof a nitrogen-containing heterocyclic ring whose nitrogen atom is notoxidated. These polymers can further have another repeating unit, forexample a repeating unit conventionally known as the one forming πconjugated macromolecule such as a (thiophen-2,5-diyl) unit.

In the copolymer of the above formula (2), the repeating unit of anitrogen-containing heterocyclic ring whose nitrogen atom is oxidatedand the repeating unit of a nitrogen-containing heterocyclic ring whosenitrogen atom is non-oxidated are copolymerized at random.

The subgroup of the N-oxidated poly(nitrogen-containing heterocyclicring) represented by the above formula (1) include N-oxidatedpoly(pyridinediyl), poly(pyrazinediyl), poly(pyrimidi nediyl), andpoly(pyridazinediyl) represented by the following formula (1a), (1b),(1c), and (1d), respectively:

wherein the degree of polymerization n₁, n₂, n₃, and n₄ represent atleast 5 and (α₁, β₁, and γ₁ represent 0 or 1.

The subgroup of the N-oxidated poly(nitrogen-containing heterocyclicring) represented by the above formula (2) include N-oxidatedpoly(pyridinediyl), poly(pyrazinediyl), poly (pyrimidinediyl), andpoly(pyridazinediyl) copolymers represented by the following formula(2a), (2b), (2c), and (2d), respectively:

wherein the degree of polymerization 1₁+m₁, 1₂+m₂, 1₃+m₃, and 1₄+m₄represent at least 5 and α₂, β₂ and γ₂ represent 0 or 1.

The N-oxidated poly(nitrogen-containing condensed heterocyclic ring) isa polymer containing a polymer chain represented by the formula (7):

wherein two of any of a, b, c, d, e, f, g and h represent carbon atomsthat are involved in binding between repeating units, at least one ofthem represents an N→O group, the remainings independently represent aCH group or a nitrogen atom, the maximum total number of the N→O groupsrepresented by a, b, c, and d is 2, the maximum total number of thenitrogen atoms is 3, the maximum total number of the N→O groupsrepresented by e, f, g, and h is 2, the maximum total number of thenitrogen atoms is 3, and the degree of polymerization n is at least 5,or a polymer containing a polymer chain represented by the formula (8):

wherein two of any of a, b, c, d, e, f, g, and h represent carbon atomsthat are involved in binding between repeating units, at least one ofthem represents an N→O group, the remainings independently represent aCH group or a nitrogen atom, the maximum total number of the N→O groupsrepresented by a, b, c, and d is 2, the maximum total number of thenitrogen atoms is 3, the maximum total number of the N→O groupsrepresented by e, f, g, and h is 2, the maximum total number of thenitrogen atoms is 3, two of any of o, p, q, r, s, t, u, and v representcarbon atoms that are involved in binding between repeating units, theremainings independently represent a CH group or a nitrogen atom, themaximum total number of the nitrogen atoms represented by o, p, q, and ris 3, the maximum total number of the nitrogen atoms represented by s,t, u, and v is 3, and the degree of polymerization 1+m is at least 5.

The subgroup of the N-oxidated poly(nitrogen-containing condensedheterocyclic ring) represented by the above formula (7) includeN-oxidated poly(quinolinediyl), poly(quinoxalinediyl), andpoly(naphthyridinediyl) represented by the following formula (7a),(7b-1), (7b-2), (7c-1), and (7c-2), respectively:

wherein the degree of polymerization n_(1.) n₂, n_(3.) n₄, and n₅represent at least 5.

The subgroup of the N-oxidated poly(nitrogen-containing condensedheterocyclic ring) represented by the above formula (8) includeN-oxidated poly(quinolinediyl), poly(quinoxalinediyl), andpoly(naphthyridinediyl) copolymers represented by the following formula(8a), (8b-1), (8b-2), (8c-1), and (8c-2), respectively:

wherein the degree of polymerization 1₁+m₁, 1₂+m₂, 1₃+m₃, 1₄+m₄, and1₅+m₅ represent at least 5.

The polymer of the above formula (7) is a polymer mainly containing arepeating unit of a nitrogen-containing condensed heterocyclic ringwhose nitrogen atom is oxidated and the polymer of the above formula (8)is a copolymer containing a repeating unit of a nitrogen-containingheterocyclic ring whose nitrogen atom is oxidated and a repeating unitof a nitrogen-containing heterocyclic ring whose nitrogen atom is notoxidated. These polymers can further have another repeating unit, forexample a repeating unit conventionally known as the one forming πconjugated macromolecule such as a (thiophen-2,5-diyl) unit.

In the copolymer of the above formula (8), the repeating unit of anitrogen-containing condensed heterocyclic ring whose nitrogen atom isoxidated and the repeating unit of a nitrogen-containing condensedheterocyclic ring whose nitrogen atom is not oxidated are copolymerizedat random.

The degree of polymerization of the polymer group of the above formulae(1), (2), (7), and (8) ranges from 5 to 1,000, preferably 5 to 500,particularly preferably 10 to 250. If the degree of polymerization isless than 5, the polymer cannot sufficiently exhibit its function as apolymer.

The method of producing the polymer of the present invention will bedescribed below.

Production Method (I)

N-oxidated poly(nitrogen-containing heterocyclic ring) can be producedby reacting poly(nitrogen-containing heterocyclic ring) containing as aconstitutive unit divalent groups represented by the formula (3):

wherein o, p, q. r, s, and t have the same meaning as described above,and the degree of polymerization x is at least 5, particularlypoly(pyridinediyl), poly(pyrazinediyl), poly(pyrimidinediyl), orpoly(pyridazinediyl), which contains as a constitutive unit divalentgroups represented by the formula (3a), (3b), (3c), or (3d):

wherein the degree of polymerization x₁, x₂, x₃, and x₄ are each atleast 5, with an appropriate peroxide, such as peracetic acid (hydrogenperoxide and glacial acetic acid), persulfuric acid, orm-chloroperbenzoic acid, to N-oxidate the nitrogen atoms in the ring.

The peroxide to be used in this reaction is not limited to theabove-described examples. Either the compounds of the formula (1) or(2), namely the formula (1a) or (2a), the formula (1b) or (2b), theformula (1c) or (2c), and the formula (1d) or (2d), can be producedselectively by altering the type and the amount of peroxide to be used,and the reaction conditions.

Similarly, N-oxidated poly(nitrogen-containing condensed heterocyclicring) can be produced by reacting poly (nitrogen-containing condensedheterocyclic ring) containing as a constitutive unit divalent groupsrepresented by the formula (9):

wherein o, p, q. r, s, t, u, and v have the same meaning as describedabove, and the degree of polymerization x is at least 5, particularlypoly(quinolinediyl), poly(quinoxalinediyl), or poly(naphthyridinediyl),which contains as a constitutive unit divalent groups represented by theformula (9a), (9b), or (9c):

wherein the degree of polymerization x₁, x₂, and x₃ are each at least 5,with an appropriate peroxide, such as peracetic acid (hydrogen peroxideand glacial acetic acid), persulfuric acid, or m-chloroperbenzoic acid,to N-oxidate the nitrogen atoms in the ring.

The peroxide to be used in this reaction is not limited to theabove-described examples. Either the compounds of the formula (7) or(8), namely the formula (7a) or (8a), the formula (7b-1) or (8b-1), theformula (7b-2) (8b-2), the formula (7c-1) or (8c-1), and the formula(7c-2) or (8c-2), can be produced selectively by altering the type andthe amount of peroxide to be used, and the reaction conditions.

Production Method II

Another method of producing N-oxidated poly (nitrogen-containingheterocyclic ring) of the present invention includes a method ofreacting a dihalide derivative represented by the formula (4):

wherein X and Y represent a halogen atom, two of any of a, b, c, d, e,and f represent carbon atoms that bind to said halogen atoms, at leastone of them represents an N→O group, the remainings independentlyrepresent a CH group or a nitrogen atom, the maximum total number of theN→O groups represented by a, b, c, d, e, and f is 2, and the maximumtotal number of the nitrogen atoms is 3, particularly a dihalidederivative that is pyridine oxide, pyrazine monooxide and dioxide, andpyrimidine monooxide and dioxide, or pyridazine monooxide and dioxide,whose any of two hydrogen atoms are substituted with halogen atoms,which is represented by the formula (4a), (4b), (4c), or (4d):

wherein X and Y each represents a halogen atom and α₃, β₃. and γ₃represent 0 or 1, with a zerovalent nickel compound.

N-oxidated poly(nitrogen-containing condensed heterocyclic ring) can beproduced in the same manner as described above by reacting a dihalidederivative represented by the formula (10):

wherein X and Y each represents a halogen atom, two of any of a, b, c,d, e, f, g, and h represent carbon atoms that bind to said halogenatoms, at least one of them represents an N→O group, the remainingsindependently represent a CH group or a nitrogen atom, the maximum totalnumber of the N→O groups represented by a, b, c, and d is 2, and themaximum total number of the nitrogen atoms is 3, the maximum totalnumber of the N→O groups contained in e, f, g, and h is 2, and themaximum total number of the nitrogen atoms is 3, particularly a dihalidederivative in which any two hydrogen atoms of quinoline oxide,quinoxaline oxide, quinoxaline dioxide, 1,5-naphthyridine oxide, or1,5-naphthyridine dioxide are substituted with halogen atoms andrepresented by the formula (10a), (10b-1), (10b-2), (10c-1), or (10c-2):

wherein X and Y each represents a halogen atom, with a zerovalent nickelcompound.

According to the above production method (II), the polymer is obtainedby reacting the dihalide derivative with an equimolar or more amount ofa zerovalent nickel compound in an organic solvent to effectdehalogenation. A suitable reaction temperature is within roomtemperature to about 80° C. and the reaction completes for about 24hours. As the above-described organic solvent, N,N-dimethylformamide,acetonitrile, toluene, tetrahydrofuran, and the like can be used.

The zerovalent nickel compound takes halogen from a haloaromaticcompound to cause a coupling reaction between aromatic groups (forexample, “Synthesis”, page 736 (1984)).

This reaction can be shown by the reaction formula (A):

Ar—X+Ar′—X+NiLm→Ar—Ar′+NiX₂Lm  (A)

wherein Ar and Ar′ represent an aromatic group, X represents a halogenatom, and L represents a neutral ligand, thus NiLm represents azerovalent nickel compound.

Accordingly, the polymer can be obtained by reacting an aromaticcompound having two halogen atoms in the molecule, namely theabove-described dihalide derivative with an equimolar or more amount ofthe zerovalent nickel compound to effect the dehalogenation reactionrepresented by the reaction formula (B) and the reaction formula (C):

2·Y—Ar″—X+NiLm→Y—Ar″—Ar″—X+NiXYLm  (B)

Y—(Ar″)n₁—X+Y—(Ar″)n₂—X+NiLm→Y—(Ar″)n₁+n₂—X+NiXYLm  (C)

wherein Y—Ar″—X represents the above-described dihalide derivative.

In the above-described reaction, a zerovalent nickel compound that issynthesized in the reaction system (so-called in situ) immediatelybefore the polymerization reaction can be used as it is as well as onesynthesized and isolated in advance. Such a zerovalent nickel compoundis, for example, a nickel complex produced by a reduction reaction or aligand exchange reaction in the presence of a neutral ligand. Examplesof the ligand include 1,5-cyclooctadiene, 2,2′-bipyridine,triphenylphosphine, and the like.

Production Method III

N-oxidated poly(nitrogen-containing heterocyclic ring) of the presentinvention can be produced by electrolytic reduction of a dihalidederivative represented by the formula (4) in which any two of hydrogenatoms of the nitrogen-containing heterocyclic compound, whose nitrogenatom constituting the ring is N-oxidated, are substituted with a halogenatoms:

wherein X and Y each represents a halogen atom and any two of a, b, c,d, e, and f represent carbon atoms that are bound to the above-describedhalogen atom and at least one of them represents an N→O group, theremainings independently represent a CH group or a nitrogen atom, themaximum total number of the N→O group represented by a, b, c, d, e, andf is 2, and the maximum total number of the nitrogen atoms is 3,particularly the formula (4a), (4b), (4c), or (4d) in which any two ofhydrogen atoms of pyridine oxide, pyrazine mono- and dioxide, pyrimidinemono- and dioxide, or pyridazine mono- and dioxide are substituted withhalogen atoms:

wherein X and Y each represents a halogen atom and α₃, β₃, and γ₃represent 0 or 1, in the presence of a nickel compound.

N-oxidated poly(nitrogen-containing condensed heterocyclic ring) can beproduced in the same manner as described above by electrolytic reductionof a dihalide derivative represented by the formula (10) in which anytwo of hydrogen atoms of a nitrogen-containing condensed heterocycliccompound, whose nitrogen atom constituting the ring is N-oxidated, aresubstituted with a halogen atom:

wherein X and Y each represents a halogen atom, any two of a, b, c, d,e, f, g, and h represent carbon atoms that bind to said halogen atoms,at least one of them represents an N→O group, the remainingsindependently represent a CH group or a nitrogen atom, the maximum totalnumber of the N→O groups represented by a, b, c, and d is 2, and themaximum total number of the nitrogen atoms is 3, the maximum totalnumber of the N→O groups represented by e, f, g, and h is 2, and themaximum total number of the nitrogen atoms is 3, particularly theformula (10a), (10b-1), (10b-2), (10c-1), or (10c-2) in which any two ofthe hydrogen atoms of quinoline oxide, quinoxaline oxide, quinoxalinedioxide, 1,5-naphthyridine oxide, or 1,5-naphthyridine dioxide aresubstituted with halogen atoms:

wherein X and Y each represents a halogen atom, in the presence of anickel compound.

In the above production method (III), when the dihalidederivative issubjected to the electrolytic reduction reaction in the presence of thedivalent nickel compound, N-oxidated poly(nitrogen-containingheterocyclic ring) can be obtained by the dehalogenation reaction.

These reactions can be expressed by the reaction formula (D), (E), (F),and (G).

[Ni¹ ¹Lm]²⁺+2e→Ni⁰Lm  (D)

Ni⁰Lm+Y—Ar″—X→Y—Ni¹ ¹Lm—Ar″—X  (E)

2·Y—Ni¹ ¹Lm—Ar″—X+2e→Y—Ar″—Ar″—X+Ni⁰Lm+X⁻+Y⁻  (F)

Y—(Ar″)n₁—X+Y—(Ar″)n₂—X+2eNi⁰Lm→Y—(Ar″)n₁+n₂—X+X⁻+Y⁻  (G)

wherein Y—Ar″—X represents the above-described dihalide derivative.

A zerovalent nickel compound is formed by electrolytic reduction of adivalent nickel compound in an electrolytic reactor. Therefore,electrolytic reduction of an aromatic compound having two halogen atomsin the molecule, namely the above-described dihalide derivative in thepresence of the divalent nickel compound results in formation of thezerovalent nickel compound and polymer can be obtained by the reactioninvolving Ni⁰Lm subsequently formed in the reaction system.

Electrolysis can be carried out under the usual conditions as describedbelow. Namely, for example, N-dimethylformamide or acetonitrile is usedas a solvent, tetraethylammonium perchlorate or tetraethylammoniumtetrafluoroborate is dissolved as a supporting electrolyte to give anelectrolytic solution, a platinum electrode, an ITO transparentelectrode, or a graphite electrode is used as an electrode. Theabove-described dihalide derivative and the divalent nickel compound isdissolved in the electrolytic solution, followed by electrolyticreduction at a reduction potential of the divalent nickel compound (forexample, −1.7 V (against Ag/Ag⁺) when tris(2,2-bipyridine) nickel saltis used).

As the above nickel compound, one synthesized and isolated previouslybefore the polymerization reaction may be used or one synthesized fromnickel or a nickel compound directly in the electrolytic reactor may beused as it is. Such a nickel compound includes, for example,tris(2,2′-bipyridine) nickel bromide (Ni(bpy)₃Br₂),dibromobis(triphenylphosphin)nickel (NiBr₂(PPh₃)₂), and the like.

N-oxidated poly(nitrogen-containing heterocyclic ring) represented bythe formula (1) or (2) according to the present invention:

wherein a, b, c, d, e, and f have the same meaning as described aboveand the degree of polymerization n is at least 5,

wherein a, b, c, d, e, f, o, p, q, r, s, and t have the same meaning asdescribed above and the degree of polymerization 1+m is at least 5,

wherein a, b, c, d, e and f have the same meaning as described above,

wherein o, p, q, r, s, and t have the same meaning as described above,is exemplified by the following in terms of the repeating units (5) and(6), but the present invention is not limited thereto.

Formula (5):

Further, N-oxidated poly(nitrogen-containing condensed heterocyclicring) represented by the formula (7) or (8) according to the presentinvention:

wherein a, b, c, d, e, f, g, and h have the same meaning as describedabove and the degree of polymerization n is at least 5,

wherein a, b, c, d, e, f, g, h, o, p, q, r, s, t, u, and v have the samemeaning as described above and the degree of polymerization 1+m is atleast 5, is exemplified by the repeating unit represented by theformulae (11) and (12):

wherein a, b, c, d, e, f, g, and h have the same meaning as describedabove,

wherein o, p, q, r, s, t, u, and v have the same meaning as describedabove, but the present invention is not limited thereto.

Formula (11):

The N-oxidated poly(nitrogen-containing a heterocyclic ring) and theN-oxidated poly(nitrogen-containing condensed heterocyclic ring) have aresonance structure as shown as an example by the formulae (13) and (14)and the formulae (15) and (16). When including an adjacent unit, thestructure having a quinoid type bond is formed and it is considered thatsuch a resonance structure is spread in the whole polymer along the πconjugated system. In the formulae (13) and (14), “ - - - ” means that amacromolecular chain is bound to the left and right sides.

The change of the main chain structure produced by the quinoid structureis analogous to the change in structure during the doping reaction.

The polymer of the present invention can be applied to fibers or films,electrochromic device, semiconductors, and active materials orelectrodes of battery, making use of its excellent properties. Also, thecompound of the present invention has conductivity by itself andfurther, is reduced by a reducing agent or by electrochemical doping toutilize as n-type semiconductor. Furthermore, when the polymer of thepresent invention is molded into a molding product, such as fiber, filmor the like, such as a heat stabilizer, a photostabilizer, a filler, ora reinforcing agent can be mixed appropriately.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the resistance measuring device based on the two probemethod used in Examples 4 to 6.

FIG. 2 shows cyclicvoltamogram obtained in Example 4.

FIG. 3 shows cyclicvoltamogram obtained in Example 5.

MODE FOR CARRYING OUT THE INVENTION

The present invention will be described below specifically and in detailwith reference to Examples, but is not limited thereto.

EXAMPLE 1 Synthesis of poly(pyridine-2,5-diyl)

Twenty ml of N,N-dimethylformamide was added to 1.53 g (5.74 mmol) ofbis(1,5-cycroctadiene)nickel under nitrogen atmosphere. Further, 0.62 gof 1,5-cyclooctadiene, 0.87 g (5.8 mmol) of 2,2′-bipyridine, and 1.1 g(4.6 mmol) of 2,5-dibromopyridine were added thereto and the mixture wasstirred at 60° C. for 8 hours under heating. The polymer thus formed waswashed with hot toluene, a warm aqueous solution ofethylenediaminetetraacetic acid (once each at pH 3 and pH 9), a warmaqueous solution of NaOH (pH=9), warm water, and hot benzene, followedby drying under reduced pressure. Thus, yellow poly(pyridine-2,5-diyl)having a molecular weight (Mw) of 4300 and the degree of polymerizationof 49, and represented by the formula (3a-A):

wherein x₁ a represents the degree of polymerization, was obtained in ayield of approximately 100%.

Synthesis of poly(pyridine-1-oxide-2,5-diyl)

One hundred mg of poly(pyridine-2,5-diyl) was suspended in 20 ml ofglacial acetic acid and 8 ml of a 30% hydrogen peroxide aqueous solutionwas added dropwise thereto at room temperature, followed by stirring at60° C. for 3 days. After allowing the mixture to cool, the yellowishbrown solid thus formed was filtered under reduced pressure and theresulting solid was successively washed with an aqueous solution ofsodium hydroxide, an aqueous solution of hydrochloric acid, and water,followed by drying under reduced pressure. Thus,poly(pyridine-1-oxide-2,5-diyl) represented by the formula (1a-A):

wherein n₁ a represents the degree of polymerization, was obtained inthe form of yellowish brown powder in a yield of 28%. The reason why theyield was low is considered that a part of the product was lost duringwashing or the other steps when the polymer was purified to improve itssolubility as described below.

The elemental analysis of the polymer represented by theformula (1a-A)resulted in carbon: 53.2%; hydrogen: 3.8%; and nitrogen: 12.1%, whichwas a polymer (calculated: carbon: 53.6%; hydrogen: 4.6%; nitrogen:12.5%, and oxygen: 29.3%) containing 1.05 water molecule per monomerunit and having a constituting unit represented by the formula:

which revealed that N-oxidation proceeded approximately 100%. The degreeof polymerization of the polymer was 49.

Comparing the characteristics of infrared absorption spectrum (IRspectrum, KBr pellet method) and ultraviolet visible absorption spectrum(UV spectrum, in a formic acid solution) of the polymer of formula(1a-A) with those of the polymer of formula (3a-A), IR spectrum of theformer shows absorption of the pyridine skeleton at 1,400 to 1,600 cm⁻¹that was slightly broader and absorption intensity that was alsochanged. Further, there observed absorption of N-oxide at about 1,240cm⁻¹ and broad shoulder absorption of water attached to the polymer atabout 1,650 cm⁻¹.

On the other hand, UV spectrum showed the maximum absorbed wave lengthof the polymer of the formula (1a-A) at 330 nm in formic acid. Comparingthis value with the maximum absorbed wave length of the polymer of theformula (3a-A), it was found that the maximum absorbed wave length wasshifted by 50 nm toward the short wave length side by N-oxidation.

Solubility in various solvents of the polymer represented by the formula(1a-A) was studied using 1 mg of the polymer and 1 ml of a solvent atroom temperature. As a result, the polymer was soluble in 28% aqueousammonia, formic acid, sulfuric acid, N,N-dimethylformamide (DMF),N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), and the like. Thus,solubility in solvents of this polymer was superior to that of thepolymer represented by the formula (3a-A) (which is soluble in formicacid and sulfuric acid, but was insoluble in usual organic solvents suchas DMF, NMP, DMSO, or the like).

EXAMPLE 2 Synthesis of poly(quinoline-2,6-diyl)

Thirty ml of N,N-dimethylformamide was added to 0.67 g (2.43 mmol) ofbis(7,5-cyclooctadiene)nickel under nitrogen atmosphere. Further, 0.35ml of 1,5-cyclooctadiene, 0.30 g (1.92 mmol) of 2,2′-bipyridine, and0.32 g (1.59 mmol) of 2,6-dichloroquinoline were added thereto and themixture was stirred at 60° C. for 48 hours under heating. The polymerthus formed was washed twice with aqueous ammonia, three times with anaqueous solution of ethylenediaminetetraacetic acid, twice with aqueousammonia, once with water, and once with methanol, followed by dryingunder reduced pressure. Thus, yellow poly(quinoline-2,6-diyl) having amolecular weight (Mw) of 15,000 and the degree of polymerization of 118,and represented by the formula (9a-A):

wherein x₁ a represents the degree of polymerization, was obtained in ayield of 99%.

Synthesis of poly(quinoline-1-oxide-2,6-diyl)

One hundred mg of poly(quinoline-2,6-diyl) was suspended in 20 ml ofglacial acetic acid and 8 ml of a 30% hydrogen peroxide aqueous solutionwas added dropwise thereto at room temperature, followed by stirring at60° C. for 3 days. After allowing the mixture to cool, the orange solidthus formed was filtered under reduced pressure and the resulting solidwas successively washed with an aqueous solution of sodium hydroxide, anaqueous solution of hydrochloric acid, and water, followed by dryingunder reduced pressure. Thus, poly(quinoline-1-oxide-2,6-diyl)represented by the formula (7a-A):

wherein n₁ a represents the degree of polymerization, was obtained inthe form of yellowish brown powder in a yield of 21%. The reason why theyield was low is considered that a part of the product was lost duringwashing or the other steps when the polymer was purified to improve itssolubility as described below.

The elemental analysis of the polymer represented by theformula (7a-A)resulted in carbon: 71.0%; hydrogen: 3.7%; and nitrogen: 9.2%, which wasa polymer (calculated: carbon: 71.1%; hydrogen: 4.0%; nitrogen: 9.2%,and oxygen: 15.7%) containing 0.49 water molecule per monomer unit andhaving a constituting unit represented by the formula:

which revealed that N-oxidation proceeded approximately 100%. The degreeof polymerization was 118.

Comparing the characteristics of infrared absorption spectrum (IRspectrum, KBr pellet method) and ultraviolet visible absorption spectrum(UV spectrum, in a formic acid solution) of the polymer of formula(7a-A) with those of the polymer of formula (9a-A), IR spectrum of theformer showed absorption of the quinoline skeleton at 1,400 to 1,600cm⁻¹ that was slightly broader and absorption intensity that was alsochanged. Further, there observed absorption of N-oxide at about 1,240cm⁻¹ and broad shoulder absorption of water attached to the polymer atabout 1,650 cm⁻¹.

On the other hand, UV spectrum showed the maximum absorption wave lengthof the polymer of the formula (7a-A) at 407 nm in formic acid. Comparingthis value with the maximum absorbed wave length of the polymer of theformula (9a-A), it was found that the maximum absorbed wave length wasshifted by 30 nm toward the short wave length side by N-oxidation.

Solubility in various solvents of the polymer represented by the formula(7a-A) was studied using 1 mg of the polymer and 1 ml of a solvent atroom temperature. As a result, the polymer was soluble in water, anaqueous solution of sodium hydroxide, formic acid, sulfuric acid,N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP),dimethylsulfoxide (DMSO), and the like. Thus, solubility in solvents ofthis polymer was superior to that of the polymer represented by theformula (9a-A) (which was soluble in formic acid and sulfuric acid, butis insoluble in usual organic solvents such as DMF, NMP, DMSO, or thelike).

Further, proton NMR spectrum of poly (quinoline-1-oxide-2,6-diyl) (7a-A)obtained in this Example was compared with that of the startingmaterial, poly(quinoline-2,6-diyl) (9a-A). Both spectra were measured intrifluoroacetic acid-d¹. As a result, absorption (delta about 9.4 ppm)of proton at position 4 of the polymer of the formula (9a-A)disappeared, while, in the case of the polymer of the formula (7a-1),absorption at delta about 9.6 ppm and delta about 9.34 ppm newlyappeared, which revealed that the electric structure of the quinolinehas been changed widely.

EXAMPLE 3 Synthesis of poly(naphthyridine-2,6-diyl)

Twelve ml of N,N-dimethylformamide was added to 0.18 g (0.65 mmol) ofbis(7,5-cyclooctadiene)nickel under nitrogen atmosphere. Further, 0.14ml of 1,5-cyclooctadiene, 0.11 g (0.72 mmol) of 2,2′-bipyridine, and0.11 g (0.53 mmol) of 2,6-dichloro-1,5-naphthyridine were added theretoand the mixture was stirred at 60° C. for 48 hours under heating. Thepolymer thus formed was washed in the same manner as in Example 2.

Thus, yellow poly(naphthyridine-2,6-diyl) represented by the formula(9c-A):

wherein x₁ a represents the degree of polymerization, was obtained in ayield of 97%. The result of halogen analysis (0.3%) revealed that themolecular weight and the degree of polymerization of the polymer were23,700 and 185, respectively.

Synthesis of poly(naphthyridine-1,5-dioxide-2,6-diyl)

Seventy mg of poly(naphthyridine-2,6-diyl) was suspendedin 20 ml ofglacial acetic acid and 8 ml of a 30% hydrogen peroxide aqueous solutionwas added dropwise thereto at room temperature, followed by stirring at60° C. for 3 days. After allowing the mixture to cool, the orange solidthus formed was filtered under reduced pressure and the resulting solidwas successively washed with an aqueous solution of sodium hydroxide, anaqueous solution of hydrochloric acid, and water. Then, the solid wasdried under reduced pressure to obtainpoly(naphthyridine-1,5-dioxide-2,6-diyl) represented by the formula(7c-2-A):

wherein n₅ a represents the degree of polymerization, was obtained inthe form of reddish brown powder in a yield of 33%. The elementalanalysis of the polymer represented by theformula (7c-2-A) resulted incarbon: 56.3%; hydrogen: 2.9%; and nitrogen 16.4%, which was a polymer(calculated: carbon: 57.4%; hydrogen: 2.9%; nitrogen: 16.7%, and oxygen:23.0%) containing 0.41 water molecule per monomer unit and having aconstituting unit represented by the formula:

which revealed that N-oxidation proceeded approximately 100%. The degreeof polymerization was 185.

Comparing the characteristics of infrared absorption spectrum (IRspectrum, KBr pellet method) and ultraviolet visible absorption spectrum(UV spectrum, in a formic acid solution) of the polymer of formula(7c-2-A) with those of the polymer of formula (9c-A), IR spectrum of theformer shows absorption of the 1,5-naphthyridine skeleton at 1,400 to1,600 cm⁻¹ that was slightly broader and absorption intensity that wasalso changed. Further, there observed absorption of N-oxide at about1,237 cm⁻¹ and broad shoulder absorption of water attached to thepolymer at about 1,600 to 1,700 cm⁻¹.

On the other hand, UV spectrum showed the maximum absorbed wave lengthof the polymer of the formula (7c-2-A) at 404 nm in formic acid.Comparing this value with the maximum absorbed wave length of thepolymer of the formula (9c-A), it was found that the maximum absorbedwave length was shifted by 35 nm toward the short wave length side byN-oxidation.

EXAMPLE 4

Electric conductivity of poly(pyridine-1-oxide-2,5-diyl)represented bythe formula (1a-A) obtained in Example 1 was measured by subjecting thepolymer to press molding in a good state to give pellet using a pressmolding machine, cutting the resulting pellet in a shape of rectangle,and fixing between two platinum electrodes d with carbon paste as shownin FIG. 1 (two probe method).

The lengths of a, b, and c (cm) referred to in FIG. 1 were respectivelymeasured, the value of resistance R (Ω) was measured, and electricconductivity was calculated by the following formula:

σ[Scm⁻¹ ]=c/(abR)

As a result, the polymer showed electric conductivity of 3.4×10⁻⁶ Scm⁻¹,which was 8 orders or more higher than electric conductivity(10⁻¹⁴σ/Scm⁻¹ or lower) of the polymer represented by the formula(3a-A).

Further, cyclicvoltamogram (CV) of the polymer of formula(1a-A) that wascasted with formic acid on the platinum electrodes was measured (FIG.2).

The peak potentials obtained by cation doping and dedoping wereE_(p c)=−2.22 V, E_(p a)=−2.00 V (each against Ag/Ag⁺), respectively.The color of the polymer turned from yellow to dark brown by doping.

EXAMPLE 5

Electric conductivity of poly(quinoline-1-oxide-2,6-diyl) represented bythe formula (7a-A) obtained in Example 2 was measured by subjecting thepolymer to pressure molding in a good state to give pellet using apressure molding machine, cutting the resulting pellet in a shape ofrectangle, and fixing between two platinum electrodes d with carbonpaste as shown in FIG. 1 (two terminal method).

The lengths of a, b, and c (cm) referred to in FIG. 1 were respectivelymeasured, the value of resistance R (Ω) was measured, and electricconductivity was calculated by the following formula:

σ[Scm⁻¹ ]=c/(abR)

As a result, the polymer showed electric conductivity of 2.3×10⁻⁶ Scm⁻¹,which was about 4 orders higher than electric conductivity (4.0×10⁻¹⁰Scm⁻¹) of the polymer represented by the formula (9a-A).

Further, cyclic voltagram (CV) of the polymer of formula(7a-A) that wascasted with formic acid on the platinum electrodes was measured (FIG.3).

The peak potentials obtained by cation doping and dedoping wereE_(p c)=−2.31 V, E_(p a)=−2.00 V (each against Ag/Ag⁺), respectively.The color of the polymer turned from yellow to violet by doping.

EXAMPLE 6

Electric conductivity of poly(naphthyridine-1,5-dioxide-2,6-diyl)represented by the formula (7c-2-A) obtained in Example 3 was measuredin the same manner as in Example 5.

As a result, the polymer showed electric conductivity of 3.2×10⁻⁶ Scm⁻¹,which was about 3 orders higher than electric conductivity (1.1×10⁻⁹Scm⁻¹) of the polymer represented by the formula (9c-A).

The novel N-oxidated poly(nitrogen-containing heterocyclic ring),particularly N-oxidated poly(pyridinediyl), and N-oxidatedpoly(nitrogen-containing condensed heterocyclic ring), particularlyN-oxidated poly(quinolinediyl), poly(quinoxalinediyl), orpoly(naphthyridinediyl), have heat resistance and are soluble in aqueousor organic solvents. Accordingly, they can be applied in various fieldsand used widely. They are dissolved in an appropriate solvent and theresulting solution can be converted into fibers, films, and the like bydry molding. These polymers also have such excellent properties thattheir degree of depolarization and electrochemical oxidation-reductionpotential can be controlled depending on their structure, whichproperties cannot be found in the conventional poly(arylene).

Further, according to the method of the present invention, it ispossible to synthesize a macromolecule in which charges resulted fromN-oxidation are nonlocalized along the π conjugated system. It was foundthat the macromolecule of the present invention has conductivity byitself.

What is claimed is:
 1. N-oxidated poly(nitrogen-containing heterocyclicring) containing a polymer chain represented by the formula (1):

wherein any two of a, b, c, d, e, and f represent carbon atoms that areinvolved in binding between repeating units, at least one of themrepresents an N→O group, the remainings independently represent a CHgroup or a nitrogen atom, the maximum total number of the N→O groupsrepresented by a, b, c, d, e, and f is 2, the maximum total number ofthe nitrogen atoms is 3, and the degree of polymerization n is at least5.
 2. N-oxidated poly(nitrogen-containing heterocyclic ring) containinga polymer chain represented by the formula (2):

wherein any two of a, b, c, d, e, and f represent carbon atoms that areinvolved in binding between repeating units, at least one of themrepresents an N→O group, the remainings independently represent a CHgroup or a nitrogen atom, the maximum total number of the N→O groupsrepresented by a, b, c, d, e, and f is 2, the maximum total number ofthe nitrogen atoms is 3, any two of o, p, q, r, s, and t representcarbon atoms that are involved in binding between repeating units, theremainings independently represents a CH group or a nitrogen atom, themaximum total number of the nitrogen atoms contained in o, p, q, r, s,and t is 3, and the degree of polymerization 1+m is at least
 5. 3. TheN-oxidated poly(nitrogen-containing heterocyclic ring) as claimed inclaim 1, wherein said formula (1) is the formula (1a), (1b), (1c), or(1d):

wherein the degree of polymerization n₁, n₂, n₃, and n₄ represent atleast 5 and α₁, β₁, and γ₁ represent 0 or
 1. 4. The N-oxidatedpoly(nitrogen-containing heterocyclic ring) as claimed in claim 2,wherein said formula (2) is the formula (2a), (2b), (2c), or (2d):

wherein the degree of polymerization 1₁+m₁, 1₂+m₂, 1₃+m₃, and 1₄+m₄represent at least 5 and α₂, β₂, and γ₂ represent 0 or
 1. 5. A method ofproducing the N-oxidated poly(nitrogen-containing heterocyclic ring) asclaimed in claim 4, which comprises reacting poly(nitrogen-containingheterocyclic ring) containing a polymer chain represented by the formula(3):

wherein o, p, q, r, s, and t have the same meaning as described aboveand the degree of polymerization x represents at least 5, with peroxideto N-oxidate the nitrogen atom in the ring.
 6. A method of producing theN-oxidated poly(nitrogen-containing heterocyclic ring) as claimed inclaim 4, which comprises reacting a dihalide derivative represented bythe formula (4)

wherein X and Y represent a halogen atom, any two of a, b, c, d, e, andf represent carbon atoms that bind to said halogen atoms, at least oneof them represents an N→O group, the remainings independently representa CH group or a nitrogen atom, the maximum total number of the N→Ogroups represented by a, b, c, d, e, and f is 2, and the maximum totalnumber of the nitrogen atoms is 3, with a zerovalent nickel compound. 7.A method of producing the N-oxidated poly(nitrogen-containingheterocyclic ring) as claimed in claim 4, which comprises subjecting adihalide derivative represented by the formula (4):

wherein X and Y represent a halogen atom, any two of a, b, c, d, e, andf represent carbon atoms that bind to said halogen atoms, at least oneof them represents an N→O group, the remainings independently representa CH group or a nitrogen atom, the maximum total number of the N→Ogroups represented by a, b, c, d, e, and f is 2, and the maximum totalnumber of the nitrogen atoms is 3, to electrolytic reduction in thepresence of a nickel compound.
 8. The method of producing the N-oxidatedpoly(nitrogen-containing heterocyclic ring) as claimed in claim 5,wherein said formula (3) is the formula (3a), (3b), (3c), or (3d):

wherein the degree of polymerization x₁, x₂, x₃, and x₄ represent atleast
 5. 9. The method of producing the N-oxidatedpoly(nitrogen-containing heterocyclic ring) as claimed in claim 6,wherein said formula (4) is the formula (4a), (4b), (4c), or (4d):

wherein X and Y each represents a halogen atom and α₃, β₃, and γ₃represent 0 or
 1. 10. The method of producing the N-oxidatedpoly(nitrogen-containing heterocyclic ring) as claimed in claim 7,wherein said formula (4) is the formula (4a), (4b), (4c), or (4d):

wherein X and Y each represents a halogen atom and α₃, β₃, and γ₃represent 0 or
 1. 11. A fiber or film which is made of the N-oxidatedpoly(nitrogen-containing heterocyclic ring) as claimed in claim
 1. 12.An electrochromic element which is made of the N-oxidatedpoly(nitrogen-containing heterocyclic ring) as claimed in claim
 1. 13.An active material or electrode for a battery, which is made of theN-oxidated poly(nitrogen-containing heterocyclic ring) as claimed inclaim
 1. 14. A semiconductor which is made of the N-oxidatedpoly(nitrogen-containing heterocyclic ring) as claimed in claim
 1. 15.An n-type semiconductor prepared by reducing the N-oxidatedpoly(nitrogen-containing heterocyclic ring) as claimed in claim 1 with areducing agent or by electrochemical doping.
 16. N-oxidatedpoly(nitrogen-containing condensed heterocyclic ring) containing apolymer chain represented by the formula (7)

wherein any two of a, b, c, d, e, f, g and h represent carbon atoms thatare involved in binding between repeating units, at least one of themrepresents an N→O group, the remainings independently represent a CHgroup or a nitrogen atom, the maximum total number of the N→O groupsrepresented by a, b, c, and d is 2, the maximum total number of thenitrogen atoms is 3, the N→O groups represented by e, f, g, and h is 2,the maximum total number of the nitrogen atoms is 3, and the degree ofpolymerization n is at least
 5. 17. N-oxidated poly(nitrogen-containingcondensed heterocyclic ring) containing a polymer chain represented bythe formula (8)

wherein any two of a, b, c, d, e, f, g, and h represent carbon atomsthat are involved in binding between repeating units, at least one ofthem represents an N→O group, the remainings independently represent aCH group or a nitrogen atom, the maximum total number of the N→O groupsrepresented by a, b, c, and d is 2, the maximum total number of thenitrogen atoms is 3, the maximum total number of the N→O groupsrepresented by e, f, g, and h is 2, the maximum total number of thenitrogen atoms is 3, any two of o, p, q, r, s, t, u, and v representcarbon atoms that are involved in binding between repeating units, theremainings independently represent a CH group or a nitrogen atom, themaximum total number of the nitrogen atoms represented by o, p, q, and ris 3, the maximum total number of the nitrogen atoms contained in s, t,u, and v is 3, and the degree of polymerization 1+m is at least
 5. 18.The N-oxidated poly(nitrogen-containing condensed heterocyclic ring) asclaimed in claim 16, wherein said formula (7) is the formula (7a),(7b-1), (7b-2), (7c-1), or (7c-2):

wherein the degree of polymerization n₁, n₂, n₃, n₄, and n₅ represent atleast
 5. 19. The N-oxidated poly(nitrogen-containing condensedheterocyclic ring) as claimed in claim 17, wherein said formula (8) isthe formula (8a), (8b-1), (8b-2), (8c-1), or (8c-2):

wherein the degree of polymerization 1₁+m₁, 1₂+m₂, 1₃+m₃, 1₄+m₄, and1₅+m₅ represent at least
 5. 20. A method of producing the N-oxidatedpoly(nitrogen-containing condensed heterocyclic ring) as claimed inclaim 16, which comprises reacting the poly(nitrogen-containingcondensed heterocyclic ring) containing a polymer chain represented bythe formula (9):

wherein o, p, q, r, s, t, u, and v have the same meaning as describedabove and the degree of polymerization x represents at least 5, withperoxide to N-oxidate the nitrogen atom in the ring.
 21. A method ofproducing the N-oxidated poly(nitrogen-containing condensed heterocyclicring) as claimed claim 16, which comprises reacting a dihalidederivative represented by the formula (10):

wherein X and Y each represents a halogen atom, any two of a, b, c, d,e, f, g, and h represent carbon atoms that bind to said halogen atoms,at least one of them represents an N→O group, the remainingsindependently represent a CH group or a nitrogen atom, the maximum totalnumber of the N→O groups represented by a, b, c, and d is 2, the maximumtotal number of the nitrogen atoms is 3, the maximum total number of theN→O groups represented by e, f, g, and h is 2, and the maximum totalnumber of the nitrogen atoms is 3, with a zerovalent nickel compound.22. A method of producing the N-oxidated poly(nitrogen-containingcondensed heterocyclic ring) as claimed in any of claims 16 to 19, whichcomprises subjecting a dihalide derivative represented by the formula(10):

wherein X and Y each represents a halogen atom, any two of a, b, c, d,e, f, g, and h represent carbon atoms that bind to said halogen atoms,at least one of them represents an N→O group, the remainingsindependently represent a CH group or a nitrogen atom, the maximum totalnumber of the N→O groups represented by a, b, c, and d is 2, and themaximum total number of the nitrogen atoms is 3, the maximum totalnumber of the N→O groups represented by e, f, g, and h is 2, and themaximum total number of the nitrogen atoms is 3, to electrolyticreduction in the presence of a nickel compound.
 23. The method ofproducing the N-oxidated poly(nitrogen-containing condensed heterocyclicring) as claimed in claim 20, wherein said formula (9) is the formula(9a), (9b), or (9c):

wherein the degree of polymerization x₁, x₂, and x₃ represent atleast 5.24. The method of producing the N-oxidated poly(nitrogen-containingcondensed heterocyclic ring) as claimed in claim 21, wherein saidformula (10) is the formula (10a), (10b-1), (10b-2), (10c-1), or(10c-2):

wherein X and Y each represents a halogen atom.
 25. The method ofproducing the N-oxidated poly(nitrogen-containing condensed heterocyclicring) as claimed in claim 22, wherein said formula (10) is the formula(10a), (10b-1), (10b-2), (10c-1), or (10c-2):

wherein X and Y each represents a halogen atom.
 26. A fiber or filmwhich is made of the N-oxidated poly(nitrogen-containing condensedheterocyclic ring) as claimed in claim
 16. 27. An electrochromic devicewhich is made of the N-oxidated poly(nitrogen-containing condensedheterocyclic ring) as claimed in claim
 16. 28. An active material orelectrode for a battery, which is made of the N-oxidatedpoly(nitrogen-containing condensed heterocyclic ring) as claimed inclaim
 16. 29. A semiconductor which is made of the N-oxidatedpoly(nitrogen-containing condensed heterocyclic ring) as claimed inclaim
 16. 30. An n-type semiconductor prepared by reducing theN-oxidated poly(nitrogen-containing condensed heterocyclic ring) asclaimed in claim 16 with a reducing agent or by electrochemical doping.